US 20100148117A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2010/0148117 A1
Logan (43) Pub. Date: Jun. 17, 2010
(54) METHOD OF MAKING GLYCEROL Publication Classification
MONOESTERS (51) Int. Cl.
C09K 3/00 (2006.01)
(76) Inventor: Roger L. Logan, Newfoundland, (52) U.S. Cl. ................................................... 252A182.12
NJ (US) (57) ABSTRACT
Described is a method of producing compositions comprising
Correspondence Address: a high concentration of glycerol monoesters. The method
Intellectual Property Department entails reacting a mixture of glycerol, a fatty acid source, and
DEWITT ROSS & STEVENS S.C. water, in the absence of catalysts, at a temperature preferably
2 East Mifflin Street, Suite 600 from about 180° C. to about 300° C., a pressure preferably
Madison, WI 53703-2865 (US) from about 15 psig to 400 psig, and for a time sufficient to
yield an acid value of preferably from about 2.0 to about 7.0
in the mixture, and a hydroxyl value preferably of from about
(21) Appl. No.: 12/332,824 260 to about 460 in the mixture. The method can be used to
make lipid mixtures comprising 90 wt % or more of glycerol
monoesters. The method does not require molecular distilla
(22) Filed: Dec. 11, 2008 tion.
US 2010/O 1481 17 A1
METHOD OF MAKING GLYCEROL
MONOESTERS
FIELD OF THE INVENTION
0001. The present invention relates to a process for pro
ducing a composition comprising glycerol esters having high
monoglyceride content. The process uses water at high tem
peratures and pressures to drive esterification and trans-es
terification reactions involving glycerol and a variety offatty
acids. The process does not require molecular distillation and
yields a composition having a monoglyceride content as high
as 90% or more.
BACKGROUND OF INVENTION
0002. It is often necessary to adjust the hydrophilic/lipo
philic balance of a lipid-containing composition in favor of
higher hydrophilicity. This is conventionally accomplished
by increasing the monoglyceride content of the lipid within
the composition. Among many other uses, glycerol
monoesters and compositions containing glycerol
monoesters are typically used to emulsify lard and many other
edible products. Several methods for producing lipids with
increased monoglyceride content are known. One method is
saponification: adding an alkali such as Sodium hydroxide to
form Soaps. Another known method is to add ethoxylates of
fatty acids and fatty alcohols. However, the amount of these
additives that can be used in edible products is strictly limited.
0003. The conventional method to produce lipid compo
sitions with increased monoglyceride content (without using
chemical additives or reactions) is to molecularly distill the
monoglycerides from the diglycerides and triglycerides con
tained in a mixed lipid feedstock. Molecular distillation (also
known as short-path distillation) is capable of generating
monoglyceride-containing compositions with a monoester
content as high as 90-95%. The process, however, is slow,
expensive, and requires highly specialized equipment. The
commercial products produced by molecular distillation,
such as “MY VEROL'-brand distilled monoglycerides
(Kerry Group Services, Ltd., Kerry, Ireland) are used exten
sively in the commercial food industries. For example,
monoglyceride compositions are used to improve qualities
Such as starch complexing in baked goods, pastas and cereals;
emulsification and stability in margarine and spreads, espe
cially in low fat products; aeration in whipped toppings;
lubrication in extruded foods; anti-Staling in bakery products,
defoaming in puddings and jams, and oil stabilization in
peanut butter.
0004. The molecular distillation process is very complex.
In essence, molecular distillation is a type of vacuum distil
lation that utilizes a vacuum typically less than about 0.01
torr, and often significantly lower. At these very low pres
Sures, the mean free path of molecules is comparable to the
size of the equipment and the gaseous phase no longer exerts
significant pressure on the Substance to be evaporated. Con
sequently, the rate of evaporation no longer depends on pres
sure. Mass transport of the distillate is therefore governed by
molecular dynamics rather than fluid dynamics. Thus, a short
path between the hot surface and the cold condensation sur
face is required; hence the term “short-path' distillation is
synonymous with “molecular distillation.”
0005. The process is performed in either a Hickman spin
ning base distillation unit or, more recently, a short-path fall
ing film (or rising film) distillation unit. In order not to dam
Jun. 17, 2010
age or degrade the final product, the distillation temperature is
held to a minimum, and a vacuum is required to decrease the
internal pressure of the distillation unit to a very low level,
typically less than 5 mtorr (0.67 Pa., 6.7 dynes/cm). Because
there is only one theoretical plate in molecular distillation
units, molecular distillation is capable of distilling only about
50% of the monoglycerides in any given solution, perpass. In
other words, the separation of monoglycerides from a com
position comprising mono-, di-, and triglycerides, in a single
cycle, is woefully incomplete. Thus, obtaining a high yield of
monoesters by molecular distillation requires multiple distil
lation cycles.
0006. However, the once-distilled feed stock cannot sim
ply be passed back through the still. The once-distilled feed
stock must first be directed to a trans-esterification unit where
the content of monoesters in the feed stock is replenished.
Excess glycerol and catalysts are added to the once-distilled
feed stock (which now contains a high proportion of non
Volatile diglycerides and triglycerides) and an enriched
monoester mixture is re-generated through trans-esterifica
tion of the fatty acid side-chains in the di- and triglycerides
and the added glycerol. In effect, fatty acid side-chains are
transferred from the diglycerides and triglycerides to the
glycerol. The catalyst must then be neutralized. Then (and
only then) is the monoester-enriched feed stock ready to be
re-introduced into the molecular distillation unit for another
round of distillation. The entire process must be repeated after
each round of distillation. Multiple iterations of the distilla
tion-trans-esterification cycle are required to obtain a high
yield of monoesters by molecular distillation. As a result, the
molecular distillation process is both complex and expensive.
0007. Therefore, there remains a long-felt and unmet need
for a method to produce lipid mixtures with a very high
percentage of glycerol monoesters of fatty acids, e.g.,
monoglycerides, without the expensive equipment, low
yields, and iterative recycling steps associated with molecular
distillation.
SUMMARY OF INVENTION
0008. The present invention solves the foregoing prob
lems. The invention is a method of generating high-content
monoglycerol ester Solutions with water at high temperatures
and pressures in esterification and trans-esterification reac
tions involving glycerol and a variety of sources offatty acids.
This method is unique in that it has at least three departures
from the prior art: (1) it employs water as a solvent at elevated
temperatures and pressure; (2) involves esterification reac
tions without a catalyst; and (3) stabilizes glycerin at high
temperatures to prevent the formation of the dangerous com
pound, acrolein.
0009. Thus, the invention is directed to a method of pro
ducing a composition of matter comprising glycerol
monoesters. One version of the invention comprises reacting
a mixture comprising glycerol, a fatty acid source, and water,
in the absence of catalysts, at an elevated temperature and at
an elevated pressure wherein the glycerol and the water have
increased solubility in the fatty acid source as compared to
their respective solubilities at room temperature and atmo
spheric pressure. The mixture is then reacted for a time suf
ficient to generate a composition of matter comprising at least
about 50 wt % glycerol monoesters.
0010. The method can be implemented either batch-wise
or continuously.
US 2010/O 1481 17 A1
0011. It is preferred that the mixture be reacted at a tem
perature of from about 180° C. to about 300° C., more pref
erably from about 200° C. to about 260°C. It is also preferred
that the mixture be reacted at a pressure of from about 15 psig
to about 400 psig, more preferably from about 30 psig to
about 75 psig. It is preferred that the mixture be reacted for a
time sufficient to yield an acid value of from about 2.0 to
about 7.0 in the mixture, and a hydroxyl value of from about
260 to about 460 in the mixture. In the most preferred version
of the invention, it is preferred that the mixture be reacted for
a time Sufficient to yield a composition of matter comprising
at least about 90 wt % glycerol monoesters. After the reaction
is complete, any excess glycerol may optionally be removed
from the mixture.
0012 All of the ranges given herein (e.g., for temperature
and pressure) include any Smaller ranges encompassed within
the broadest range. Thus, for example, the pressure range
noted in the previous paragraph, about 15 psig to about 400
psig, explicitly includes Smaller encompassed ranges such as
20 to 300 psig, 100 to 200 psig, etc.
0013 The fatty acid source used in the invention can
derive from any source, without limitation. The fatty acid
Source may comprise a fatty acid in free acid form or as a
glyceride. Thus, for example, the fatty acid can comprise (by
way of example and not limitation) a purified fatty acid
selected from the group consisting of decanoic acid, lauric
acid, myristic acid, palmitic acid, pentadecanoic acid, Stearic
acid, arachidic acid, behenic acid, lignoceric acid, margaric
acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic
acid, erucic acid, ricinoleic acid, linoleic acid, linolenic acid,
licanic acid, margaroleic acid, arachidonic acid clupanadonic
acid, eicosapentaenoic acid, docosahexaenoic acid, and the
like. The fatty acid source may comprise a natural oil or fat,
Such as (but not limited to) animal fats, soya bean oil, coconut
oil, palm oil, palm kernel oil, rapeseed oil, cottonseed oil,
linseed oil, Sunflower oil, fish oil, algae oil, and the like.
DETAILED DESCRIPTION OF THE INVENTION
0014. Unless otherwise stated, the following definitions
are used throughout the present application:
00.15 Acid value' refers to the mass of potassium
hydroxide in milligrams that is required to neutralize one
gram of a chemical Substance. The acid value measures the
amount of carboxylic acid groups in a chemical solution.
With respect to the present application, the acid value pro
vides a measure of the free fatty acid groups present in the
solution. See ASTM D 1980. Acid value may also be
expressed as the number of mL of 0.1 N alkali required to
neutralize the free acids in 10.0 g of the substance. This
alternative approach is the method utilized by U.S. Pharma
copoeia: 10 g of the test sample is dissolved 50 mL of a
mixture of equal volumes of alcohol and ether which has been
neutralized to phenolphthalein by adding 0.1 N sodium
hydroxide. One (1) mL of phenolphthalein test solution (1 g
phenolphthalein in 100 ml alcohol) is then added to the solu
tion. The solution is then titrated with 0.1 N sodium hydrox
ide until the solution remains faintly pink after shaking for 30
seconds. Record the volume of 0.1 Nalkali required to neu
tralize the solution.
0016 “Fatty acid as used herein refers to an acyl chain
covalently conjugated to a carboxyl functional group. The
fatty acid may be in a “free form in which the carboxyl
group is not further covalently modified, or a 'glyceride
form,” in which the carboxyl group is further covalently
Jun. 17, 2010
bound to either the alpha or beta position of glycerol via an
ester bond. The glyceride form of a fatty acid may contain
from one to three fatty acids on any of three possible positions
on the glycerol moiety, and the type of fatty acid may be the
same or different.
(0017 “Hydroxyl value” refers to a measure of hydroxyl
(univalent —OH) groups in an organic Solution. With respect
to the present work, the hydroxyl value provides a measure of
the free glycerol present in the solution. See ASTM D1957
86(2001) and JIS K-0070. Hydroxyl value may also be deter
mined according to the USP method:
0018. The hydroxyl value is the number of mg of potas
sium hydroxide equivalent to the hydroxyl content of 1.0 g of
the substance. Pyridine-Acetic Anhydride Reagent: Just
before use, mix 3 volumes of freshly opened or freshly dis
tilled pyridine with 1 volume of freshly opened or freshly
distilled acetic anhydride.
0019 Procedure Transfer a known quantity of the sub
stance to a glass-stoppered, 25.0-mL conical flask, and add
5.0 mL of pyridine-acetic anhydride reagent. Transfer 5.0 mL
of pyridine-acetic anhydride reagent to a second, glass-stop
pered, 250-mL conical flask to provide the reagent blank. Fit
both flasks with suitable glass-jointed reflux condensers, heat
on a steam bath for 1 hour, add 10 mL of water through each
condenser, and heat on the steam bath for 10 minutes more.
Cool, and to each add 25 mL of butyl alcohol, previously
neutralized to phenolphthalein test solution with 0.5N alco
holic potassium hydroxide, by pouring 15 mL through each
condenser and, after removing the condensers, washing the
sides of both flasks with the remaining 10-mL portions. To
each flask add 1 mL of phenolphthalein test solution and
titrate with 0.5 N alcoholic potassium hydroxide, recording
the Volume, in mL, consumed by the residual acid in the test
solution as “T” and that consumed by the blank as “B” In a
125-mL conical flask, mix about 10 g of the Substance, accu
rately weighed, with 10 mL of freshly distilled pyridine,
previously neutralized to phenolphthalein test solution, add 1
mL of phenolphthalein test solution, and titrate with 0.5 N
alcoholic potassium hydroxide, recording the Volume, in mL.
consumed by the free acid in the test specimen as 'A', or use
the acid value to obtain A. Calculate the hydroxyl value by the
formula:
in which W and C are the weights, in g, of the substances
taken for the acetylation and for the free acid determination,
respectively; N is the exact normality of the alcoholic potas
sium hydroxide; and 56.11 is the molecular weight of potas
sium hydroxide.
0020) “Psig is an abbreviation for “pounds-force per
square inchgauge a unit of pressure relative to the Surround
ing atmosphere.
0021 “Glycerin’ and glycerol are used interchange
ably.
0022. The terms “glycerol ester” and “glyceride' are used
interchangeably and refer to a molecule with a glycerol back
bone with at least one fatty acid moiety conjugated thereto via
an ester bond. Monoglycerides or monoglycerol esters con
tain one fatty acid moiety; diglycerides contain two fatty acid
moieties, and triglycerides contain three fatty acid moieties.
0023 As used herein, percentages mean percent by mass.
0024. The determination of monoglyceride and diglycer
ide content by capillary gas chromatography was performed
US 2010/O 1481 17 A1
as described in the Official Methods and Recommended Prac
tices of the AOCS Cd 11b-91.
0025. Unless otherwise defined, all other technical and
Scientific terms used herein have the same meaning as com
monly understood by one of ordinary skill in the chemical art.
0026. The invention is a process that yields lipid compo
sitions comprising at least about 80% monoglyceride content,
more preferably at least about 85% monoglyceride content,
and most preferably at least about 90% total monoglyceride
content via a direct esterification reaction with fatty acids and
glycerol or via a trans-esterification reaction with glycerides
(e.g., diglycerides and triglycerides) and glycerol, in the
absence of molecular distillation. The process uses water at
high temperature and relatively modest pressure as a co
solvent for both glyceroland the fatty phase and as a stabilizer
of the glycerol. The water enhances the solubility of glycerol
in the fatty oil phase and allows the glycerol to undergo direct
esterification or trans-esterification.
0027. To achieve the desired high monoester content of the
product, the solubility of the water and glycerol in the lipid
phase must be increased. However, at ambient temperatures,
glycerol is nearly insoluble in fatty acids and/or triglycerides
Such as palm oil and Soya oil. A conventional method to
increase the solubility of glycerol in the fatty phase is to
increase the temperature to as high as 240 to 250° C. How
ever, above 250° C., the glycerol can decompose to acrolein
(Syn., acrylaldehyde), a very dangerous condition that must
be avoided. (Acrolein is a powerful pulmonary irritant and
lacrimating agent. It was used as a chemical weapon in World
War I.) Most laboratory esterification equipment and com
mercial plants are designed to operate at atmospheric pres
Sure. This limited design has prevented previous workers
from considering the benefits of using water underpressure to
increase the solubility of glycerol in the fatty phase while
preventing the decomposition of glycerol to acrolein. The
present inventors have found that at elevated temperatures,
preferably from about 180° C. to about 300° C., and more
preferably from about 200° C. to about 260° C., and relatively
modest pressure, preferably from about 15 psig to 200 psig,
more preferably 30 psig to about 100 psig, water will: (a) act
as a co-solvent for glycerol and fatty acid, (b) stabilize the
glycerol to prevent the formation of acrolein, (c) promote
direct esterification of fatty acids with glycerol without the
use of catalysts; and (d) promote trans-esterification of glyc
erol with long chain glycerides without the use of catalysts.
The result is that the process yields compositions having very
high monoester content, often as high as 90 to 95%.
0028. Acid and alkaline catalysts have been used in direct
esterification reactions with glycerol and fatty acids and
trans-esterification reactions with glycerides. However, the
catalytic approach typically yields lipid compositions having
a monoglyceride content of about 60%, with diglycerides and
triglycerides comprising the remaining 40%. The catalysts
must be carefully neutralized to prevent reverse reactions
during Subsequent rounds of distillation. The neutralization
process requires removing the salts formed by the neutraliza
tion reaction, as well as removing excess glycerol. An
unwanted result is that the neutralization and salt/glycerol
removal steps cause a loss of monoglyceride content. Thus,
the primary advantages of the invention are that no catalyst is
necessary in either the esterification or trans-esterification
reactions and molecular distillation of the product is not
required. In short, the present invention yields a composition
with a very high monoester-content, using a direct, single
Jun. 17, 2010
step reaction, without the use of acid or base catalysts, and
without using molecular distillation.
0029. The reactor required to implement the present
invention must be capable of withstanding the pressures
required generally up to at least 300 psig (although the
reaction can be performed at much lower pressures). To main
tain an adequate margin of safety, the reactor should be
capable of withstanding Sustained internal pressures of at
least about 100 to 150 psig. In a preferred design, a valve is
installed in a vapor pipe between the reactor and a condenser.
The valve in the vapor pipe is bypassed with a control valve
bypass line of sufficient size to modulate the pressure within
the reactor. In a large reactor, the vapor pipe between the
reactor and the condenser may have a diameter of from about
20 to about 30 inches (about 51 to about 76 cm), and the
control valve bypass line may have a diameter of from about
3 to 4 inches (about 8 to about 10 cm). Conventional esteri
fication reactors do not have the ability to close off the vapor
path and use a controlling bypass to the vapor condenser.
Suitable reactors are made by a large number of international
commercial Suppliers, such as Bichi AG (Uster, Germany).
0030. The fatty acid lipid feed stock to be used in the
invention can be derived from any source now known or
developed in the future, without limitation, and includes (also
without limitation) purified fatty acids, natural oils, and tal
low. The purified fatty acids can either be in a free form (i.e.,
free fatty acids) or conjugated to glycerol in a glyceride form
(i.e. mono-, di-, and/or triglycerides). The fatty acids can be
Substituted or unsubstituted, saturated or unsaturated, and
have fatty acid chain lengths of from 2 to 30, and preferably
from 10 to 30 carbon atoms, and most preferably from 10 to
22 carbon atoms. Examples of preferred fatty acids include
(without limitation) decanoic acid, lauric acid, myristic acid,
palmitic acid, pentadecanoic acid, Stearic acid, arachidic acid,
behenic acid, lignoceric acid, margaric acid, myristoleic acid,
palmitoleic acid, oleic acid, gadoleic acid, erucic acid, rici
noleic acid, linoleic acid, linolenic acid, licanic acid, marga
roleic acid, arachidonic acid clupanadonic acid, eicosapen
taenoic acid, docosahexaenoic acid, soya bean-derived fatty
acids, coconut oil-derived fatty acids, palm oil-derived fatty
acids, palm kernel-derived fatty acids, and tallow-derived
fatty acids. The natural oils can include plant and animal
derived oils, including soya bean oil, coconut oil, palm oil,
palm kernel oil, rapeseed oil, linseed oil, sunflower oil, fish
oil, and algae oil.
0031 Sufficient water must be present to act as a co
Solvent for glycerol and the fatty phase. In using fatty acids as
a feed stock, the water of reaction will be 5 to 10% depending
on the molecular weight of the fatty acid. The water of reac
tion should be sufficient to Supply enough water to act as a
co-solvent and stabilizer for the glycerol if it is not allowed to
vent from the reactor.
0032. As the fatty acid chain length is increased, the solu
bility of water and glycerol in the fatty phase decreases sub
stantially. As the fatty acid chain length approaches 20 carbon
atoms and beyond, this limits the amount of monoglycerides
that can be formed from about 40% to about 55% of total
content (by weight). It is necessary to dissolve water in the
fatty phase to the extent of about 5% to about 20% of the fatty
phase for efficient esterification to occur. To increase the
solubility of water and glycerol in the fatty phase in the case
of long-chain fats or other especially hydrophobic fats
(thereby to increase the yield of monoglycerides), the reac
tion temperature may have to be elevated to above about 200°
US 2010/O 1481 17 A1
C. Pressures in the range of 20 psig to 400 psig provide
sufficient water to accomplish this desired result. In addition,
an external source of steam or water may also be supplied.
0033. As the reaction proceeds and more glycerol
monoesters form, the fatty phase becomes increasingly more
hydrophilic. The increased hydrophilicity of the fatty phase
allows for more water to be dissolved in the fatty phase, which
increases the solubility of glycerol in the fatty phase. This
cascade of increasing hydrophilicity promotes higher
monoester content in the final product.
0034. When natural oils comprising a high concentration
of triglycerides are used as the feed Stock (Such as Soya oil,
tallow, or palm oil), no water is produced from the trans
esterification reaction. Therefore, the reaction should be
Supplemented with an external Source of water or steam and/
or an external Source of fatty acids.
0035. When the reaction is complete, the reaction is
cooled. The insoluble glycerol collects in the bottom layer
and is drawn off. The soluble glycerol is separated from the
lipid fraction by any suitable method, typically conventional
distillation. Alternatively, in large-scale installations, both the
insoluble and soluble glycerol can be distilled from the
monoesters. In yet another alternative, the excess glycerol can
be stripped from the monoesters in a high-vacuum, counter
current Stripping column.
EXAMPLES
0036. The following Examples are included solely to pro
vide a more complete understanding of the present invention.
The Examples do not limit the scope of the invention dis
closed and claimed herein in any fashion.
Example 1
Generation of a 90% Monoester Solution of Glycerol
Monolaurate by Direct Esterification Reaction
0037. A reactor was equipped with an agitator, then-no
well, pressure control valve, relief valve, cooling coils,
sample line, and vapor condenser to enable it to regulate
temperature and pressure. Unless designated otherwise,
“parts' are parts by weight. The following were charged to the
reactor at 80° C.:
0038 1000 pts. 99% glycerol:
0039) 1400 pts. lauric acid; and
004.0) 350 pts. water.
The pressure reactor was rapidly heated from 80°C. to 220
230° C. The reactor developed a pressure of 45 psig which
was slowly reduced to 30-35 psig over 2 hours. The reactor
was sampled for acid value. The acid value was 5.5. The
pressure was reduced to 15 psig while the temperature was
held at 230° C. After one hour at 15 psig and 230° C., the
pressure was reduced to atmospheric, and the reactor was
rapidly cooled to 80°C. The excess glycerol was removed
with multiple washes until the free glycerol content was
below 0.5%. The product was dried under a vacuum at 80°C.
0041. The final glycerol monolaurate solution had the fol
lowing properties:
0042. Hydroxyl value: 405 (over 90% monoester).
0043 Acid value: 2.5
0044) Melting point: 54.0° C.
0045 Free glycerol: 0.3%
Jun. 17, 2010
These results show that a 90% monoester solution of glycerol
monolaurate can be generated in a direct esterification reac
tion using the above methods.
Example 2
Generation of a 90% Monoester Solution of Glycerol
Monooleate by Direct Esterification Reaction
0046. A reactor was equipped with an agitator, thermo
well, pressure control valve, relief valve, cooling coils,
sample line, and vapor condenser to enable it to regulate
temperature and pressure. The following were charged to the
reactor at 80° C.:
0047 1000 pts. 99% glycerol:
0048. 1400 pts. oleic acid; and
0049 450 pts. water.
The pressure reactor was rapidly heated from 80°C. to 250
255°C. The reactor developed a pressure of 200 psig which
was slowly reduced to 100-110 psig over 2 hours. The reactor
was sampled for acid value. The acid value was 6.1. The
pressure was reduced to 10 psig while the temperature was
held at 250° C. After one hour at 10 psig and 250° C., the
pressure was reduced to atmospheric, and the reactor was
rapidly cooled to 170° C. The excess glycerol was removed
by distillation in a continuous counter-current stripping tower
operating at a pressure of less than 5 torr and a temperature of
170° C. with the assistance of steam.
0050. The final glycerol monooleate solution had the fol
lowing properties:
0051 Hydroxyl value: 318 (over 90% monoester).
0052 Acid value: 2.0
0053 Free glycerol: 0.4%
These results show that a 90% monoester solution of glycerol
monooleate can be generated in a directesterification reaction
using the above methods.
Example 3
Generation of a 90% Monoester Solution by Trans
Esterification Reaction with Soya Bean Oil and
Glycerol
0054. A reactor was equipped with an agitator, thermo
well, pressure control valve, relief valve, cooling coils,
sample line, high-pressure steam line through sparge ring,
and vapor condenser to enable it to regulate temperature and
pressure. The following were charged to the reactor at 80°C.:
0.055 1000 pts. 99% glycerol:
0056 1780 pts. soya oil;
0057 120 pts. soya fatty acids; and
0058 450 pts. water.
The pressure reactor was rapidly heated from 80°C. to 250°
C. The reactor developed a pressure of 125-150 psig. After six
hours, the reactor was sampled for acid value. The acid value
was 2.5. The pressure was reduced to 10 psig while the
temperature was maintained at 250° C. After 1.5 hours at 10
psig and 250° C., the pressure was reduced to atmospheric,
and the reactor was cooled to 170° C. The excess glycerol was
removed from the reactor by high vacuum distillation at a
pressure of less than 5 torr and with the assistance of dry
Steam.
0059. The final composition had the following properties:
0060 Hydroxyl value: 315 (over 90% monoester)
0061 Acid value: 1.5
0062 Free glycerol: 0.4%
US 2010/O 1481 17 A1
These results show that a 90% monoester solution can be
generated from monosoya fats in a trans-esterification reac
tion using the above methods.
Example 4
Generation of a 90% Monoester Solution of Glycerol
Monoerucate by Direct Esterification Reaction
0063 A reactor was equipped with an agitator, thermo
well, pressure control valve, relief valve, cooling coils,
sample line, and vapor condenser to enable it to regulate
temperature and pressure. The following were charged to the
reactor at 80° C.:
0064 1000 pts. 99% glycerol:
0065. 1700 pts. erucic acid; and
0066 400 pts. water.
The pressure reactor was rapidly heated from 80°C. to 250
255° C. The reactor developed a pressure of 125-150 psig
which was slowly reduced to 70-75 psig over 2 hours. The
reactor was sampled for acid value. The acid value was 6.5.
The pressure was reduced to 10 psig while the temperature
was held at 250° C. After one hour at 10 psig and 250°C., the
pressure was reduced to atmospheric, and the reactor was
rapidly cooled to 170° C. The excess glycerol was removed
from the reactor by high-vacuum distillation at a pressure of
less than 5 torr with the assistance of dry steam.
0067. The final glycerol monoerucate solution had the
following properties:
0068 Hydroxyl value: 270 (over 90% monoester).
0069. Acid value: 1.5
0070 Free glycerol: 0.4%
These results show that a 90% monoester solution of glycerol
monoerucate can be generated in a direct esterification reac
tion using the above methods.
Example 5
Generation of a 90% Monoester Solution of Glycerol
Monodecanoate by Direct Esterification Reaction
0071. A reactor was equipped with an agitator, thermo
well, pressure control valve, relief valve, cooling coils,
sample line, and vapor condenser to enable it to regulate
temperature and pressure. The following were charged to the
reactor at 80° C.:
0072 1000 pts. 99% glycerol:
0073 1100 pts. decanoic acid; and
0074) 350 pts. water.
The pressure reactor was heated rapidly from 80°C. to 210
220° C. The reactor developed a pressure of 35 psig which
was slowly reduced to 25-30 psig over 2 hours. The reactor
was sampled for acid value. The acid value was 6.0. The
pressure was reduced to 10 psig while the temperature was
held at 225° C. After one hour at 10 psig and 225°C., the
pressure was reduced to atmospheric, and the reactor was
rapidly cooled to 80°C. The excess glycerol was washed out
with multiple washes until the free glycerol content was
below 0.4%. The product was dried under a vacuum at 80°C.
0075. The final glycerol monodecanoate solution had the
following properties:
0076. Hydroxyl value: 454 (over 90% monoester).
0.077 Acid value: 2.5
0078 Free glycerol: 0.4%
Jun. 17, 2010
These results show that a 90% monoester solution of glycerol
monodecanoate can be generated in a direct esterification
reaction using the above methods.
Example 6
Generation of a 90% Monoester Solution by Trans
Esterification Reaction with Coconut Oil and Glyc
erol
0079 A reactor was equipped with an agitator, then no
well, pressure control valve, relief valve, cooling coils,
sample line, high-pressure steam line through sparge ring,
and vapor condenser to enable it to regulate temperature and
pressure. The following were charged to the reactor at 80°C.:
0080 1000 pts. 99% glycerol:
I0081. 1800 pts. coconut oil;
I0082) 140 pts. coconut fatty acids; and
I0083 400 pts. water.
The pressure reactor was heated rapidly from 80°C. to 240°
C. The reactor developed a pressure of 80-85 psig. After four
hours, the reactor was sampled for acid value. The acid value
was 2.0. The pressure was reduced to 10 psig while the
temperature was maintained at 240° C. After 1.0 hours at 10
psig and 240° C., the pressure was reduced to atmospheric,
and the reactor was cooled to 170° C. The excess glycerol was
removed by distillation in a counter-current stripping tower
operating at less than 5 torr pressure and 170° C. with the
assistance of steam.
I0084. The final coconut-oil monoglyceride product had
the following properties:
I0085) Hydroxyl value: 366 (over 90% monoester)
I0086 Acid value: 1.0
I0087 Free glycerol: 0.2%
These results show that a 90% monoester solution derived
from coconut oil and glycerol can be generated by a trans
esterification reaction using the above methods.
Example 7
Generation of a 90% Monoglyceride Solution by
Trans-Esterification Reaction with Tallow and Glyc
erol
I0088 A reactor was equipped with an agitator, thermo
well, pressure control valve, relief valve, cooling coils,
sample line, high-pressure steam line through sparge ring,
and vapor condenser to enable it to regulate temperature and
pressure. The following were charged to the reactor at 80°C.:
I0089 1000 pts. 99% glycerin;
0090 1800 pts. tallow:
0091. 140 pts. tallow fatty acids; and
0092] 425 pts. water.
The pressure reactor was heated rapidly from 80°C. to 255°
C. The reactor developed a pressure of 200-210 psig. After
four hours, the reactor was sampled for acid value. The acid
value was 3.5. The pressure was reduced to 10 psig while the
temperature was maintained at 250° C. After 1.5 hours at 10
psig and 250° C., the pressure was reduced to atmospheric,
and the reactor was cooled to 170° C. The excess glycerol was
removed by distillation in a counter-current stripping tower
operating at less than 5 tort and 170° C. with the assistance of
Steam.
0093. The final solution of monoglycerides from tallow
had the following properties:
(0094) Hydroxyl value: 309 (over 90% monoester)
0.095 Acid value: 2.3
(0096 Free glycerol 0.3
These results show that a 90% monoester solution of
monoglycerides can be generated from tallow in a trans
esterification reaction using the above methods.
US 2010/O 1481 17 A1
Example 8
Generation of a 90% Monoglyceride Solution by
Trans-Esterification Reaction with Palm Oil and
Glycerol
0097. A reactor was equipped with an agitator, thermo
well, pressure control valve, relief valve, cooling coils,
sample line, high-pressure steam line through sparge ring,
and vapor condenser to enable it to regulate temperature and
pressure. The following were charged to the reactor at 80°C.:
0098 1000 pts. 99% glycerin;
0099] 1750 pts. palm oil;
0100 145 pts. palm oil fatty acids; and
0101 450 pts. water.
The pressure reactor was heated rapidly from 80°C. to 255°
C. The reactor developed a pressure of 200 psig. After four
hours, the reactor was sampled for acid value. The acid value
was 3.0. The pressure was reduced to 10 psig while the
temperature was maintained at 250° C. After 1.5 hours at 10
psig and 250° C., the pressure was reduced to atmospheric,
and the reactor was cooled to 170° C. The excess glycerol was
removed from the reactor by high vacuum distillation with the
assistance of steam. The vacuum pressure was below 5.0 torr,
and the temperature was 170-175° C.
0102 The final palm oil monoglyceride solution had the
following properties:
(0103 Hydroxyl value: 307 (over 90% monoester)
01.04 Acid value: 2.0
0105 Free glycerol: 0.2%
These results show that a 90% monoester solution of
monoglycerides can be generated from palm oil and glycerol
in a trans-esterification reaction using the above methods.
Example 9
Generation of a 90% Monoglyceride Solution of
Glycerol Monostearate by Direct Esterification
Reaction
0106. A reactor was equipped with an agitator, thermo
well, pressure control valve, relief valve, cooling coils,
sample line, and vapor condenser to enable it to regulate
temperature and pressure. The following were charged to the
reactor at 80° C.:
0107 1000 pts. 99% glycerol:
0108. 1400 pts. Stearic acid (70% C18/30% C16); and
0109) 500 pts. water.
The pressure reactor was heated rapidly from 80°C. to 255
260° C. The reactor developed a pressure of 150-175 psig,
which was slowly reduced to 80 psig over 2 hours. The reactor
was sampled for acid value. The acid value was 6.5. The
pressure was reduced to 10 psig while the temperature was
held at 250° C. After one hour at 10 psig and 250° C., the
pressure was reduced to atmospheric, and the reactor was
rapidly cooled to 170° C.
0110. The excess glycerol was removed from the reactor
by high vacuum distillation at less than 5 torr and applying
dry steam.
0111. The final glycerol monostearate solution had the
following properties:
0112 Hydroxyl value: 320 (over 90% monoester)
0113 Acid value: 1.5
0114 Free glycerol: 0.5%
These results show that a 90% monoester solution of glycerol
monostearate can be generated by a direct esterification reac
tion using the above methods.
Jun. 17, 2010
Example 10
Generation of a 90% Monoglyceride Solution by
Trans-Esterification Reaction with Rapeseed Oil
Containing a High Content of Erucic Acid and Glyc
erol
0115 A reactor was equipped with an agitator, thermo
well, pressure control valve, relief valve, cooling coils,
sample line, and vapor condenser to enable it to regulate
temperature and pressure. The following were charged to the
reactor at 80° C.:
0116 1000 pts. 99% glycerin;
0117 1850 pts. rapeseed oil;
0118 450 pts. water.
The pressure reactor was heated rapidly from 80°C. to 250
255°C. The reactor developed a pressure of 400 psig, which
was slowly reduced to 100-110 psig over four hours. The
reactor was sampled for acid value. The acid value was 6.5.
The pressure was reduced to 10 psig while the temperature
was maintained at 250° C. After one hour at 10 psig and 250°
C., the pressure was reduced to atmospheric, and the reactor
was rapidly cooled to 170° C. The excess glycerol was
removed from the reactor by high vacuum distillation with the
assistance of dry steam at a pressure less than 5.0 torr.
0119 The final rapeseed monoglyceride solution had the
following properties:
I0120 Hydroxyl value: 285 (over 90% monoester)
0121 Acid value: 1.5
(0.122 Free glycerol: 0.6%
These results show that a 90% monoester solution of
monoglycerides can be generated from rapeseed oil and glyc
erol in a trans-esterification reaction using the above meth
ods.
Example 11
Generation of a Very-High Monoester Solution of
Glycerol Monoricinoleate by Direct Esterification
Reaction
0123. A reactor was equipped with an agitator, thermo
well, pressure control valve, relief valve, cooling coils,
sample line, and vapor condenser to enable it to regulate
temperature and pressure. The following were charged to the
reactor at 80° C.:
(0.124 1000 pts. 99% glycerol:
(0.125 1550 pts. ricinoleic acid; and
(0.126 400 pts. water.
The pressure reactor was rapidly heated from 80°C. to 250
255°C. The reactor developed a pressure of 110 psig, which
was slowly reduced to 50-55 psig over 3 hours. The reactor
was sampled for acid value. The acid value was 6.3. The
pressure was reduced to 10 psig while the temperature was
held at 150° C. After one hour at 10 psig and 250° C., the
pressure was reduced to atmospheric, and the reactor was
rapidly cooled to 160° C. The excess glycerol was removed
by distillation in a continuous counter-current stripping tower
operating at a pressure of less than 2 torr and a temperature of
160° C. with the assistance of steam.
US 2010/O 1481 17 A1
0127. The final glycerol ricinoleate solution had the fol
lowing properties (note that ricinoleic acid has a hydroxyl
group at the 12" carbon):
0128 Estimated monoglycerol content as determined by
gas chromatography: 80%
0129. Acid value: 4.1
0130 Free glycerol: 1.2%
These results show that a very-high monoester solution of
glycerol monoricinoleate can be generated in a direct esteri
fication reaction using the above methods.
What is claimed is:
1. A method of producing a composition of matter com
prising glycerol monoesters, the method comprising: reacting
a mixture comprising glycerol, a fatty acid source, and water,
and devoid of catalysts, at an elevated temperature and at an
elevated pressure wherein the glycerol and the water have
increased solubility in the fatty acid source as compared to
their respective solubilities at room temperature and atmo
spheric pressure, for a time Sufficient to generate a composi
tion of matter comprising at least about 50 wt % glycerol
monoesterS.
2. The method of claim 1, comprising reacting the mixture
at a temperature of from about 180° C. to about 300° C.
3. The method of claim 1, comprising reacting the mixture
at a temperature of from about 200° C. to about 260° C.
4. The method of any one of claims 1, 2, or 3, comprising
reacting the mixture at a pressure of from about 15 psig to
about 400 psig.
5. The method of claim 4, comprising reacting the mixture
for a time sufficient to yield an acid value of from about 2.0 to
about 7.0 in the mixture.
6. The method of claim 5, comprising reacting the mixture
for a time sufficient to yield a hydroxyl value of from about
260 to about 460 in the mixture.
7. The method of claim 6, comprising reacting the mixture
for a time sufficient to yield a composition of matter compris
ing at least about 90 wt % glycerol mono esters.
8. The method of any one of claims 1, 2, or 3, comprising
reacting the mixture at a pressure of from about 30 psig to
about 75 psig.
9. The method of claim 8, comprising reacting the mixture
for a time sufficient to yield an acid value of from about 2.0 to
about 7.0 in the mixture.
Jun. 17, 2010
10. The method of claim.9, comprising reacting the mixture
for a time sufficient to yield a hydroxyl value of from about
260 to about 460 in the mixture.
11. The method of claim 10, comprising reacting the mix
ture for a time sufficient to yield a composition of matter
comprising at least about 90 wt % glycerol monoesters.
12. The method of claim 1, further comprising, after the
reacting step, removing excess glycerol from the mixture.
13. The method of claim 1, wherein the fatty acid source
comprises a fatty acid in free acid form.
14. The method of claim 1, wherein the fatty acid source
comprises a glyceride.
15. The method of claim 1, wherein the fatty acid source
comprises a purified fatty acid selected from the group con
sisting of decanoic acid, lauric acid, myristic acid, palmitic
acid, pentadecanoic acid, Stearic acid, arachidic acid, behenic
acid, lignoceric acid, margaric acid, myristoleic acid, palmi
toleic acid, oleic acid, gadoleic acid, erucic acid, ricinoleic
acid, linoleic acid, linolenic acid, licanic acid, margaroleic
acid, arachidonic acid clupanadonic acid, eicosapentaenoic
acid, and docosahexaenoic acid.
16. The method of claim 1, wherein the fatty acid source
comprises a natural oil or fat.
17. The method of claim 1, wherein the natural oil or fat is
selected from the group consisting of animal fats, soya bean
oil, coconut oil, palm oil, palm kernel oil, rapeseed oil, cot
tonseed oil, linseed oil, Sunflower oil, fish oil, and algae oil.
18. A method of producing a composition of matter com
prising glycerol monoesters, the method comprising:
reacting a mixture comprising glycerol, a fatty acid source,
and water, and devoid of catalysts, at a temperature of
from about 180° C. to about 300° C., and a pressure of
from about 15 psig to 400 psig, for a time sufficient to
yield an acid value of from about 2.0 to about 7.0 in the
mixture, and a hydroxyl value of from about 260 to about
460 in the mixture; and then
removing excess glycerol from the mixture, thereby yield
ing a composition of matter comprising at least about 90
wt % glycerol monoesters.
c c c c c